15406 Phys. Chem. Chem. Phys.

, 2012, 14, 1540615411 This journal is c the Owner Societies 2012

Cite this: Phys. Chem. Chem. Phys., 2012, 14, 1540615411
Inuence of organic solvent on optical and structural properties
of ultra-small silicon dots synthesized by UV laser ablation in liquidw
Romuald Intartaglia,*
a
Komal Bagga,
a
Alessandro Genovese,
b
Athanassia Athanassiou,
ac
Roberto Cingolani,
a
Alberto Diaspro
a
and
Fernando Brandi
a
Received 29th June 2012, Accepted 20th September 2012
DOI: 10.1039/c2cp42195j
Ultra small silicon nanoparticles (Si-NPs) with narrow size distribution are prepared in a one step
process by UV picosecond laser ablation of silicon bulk in liquid. Characterization by electron
microscopy and absorption spectroscopy proves Si-NPs generation with an average size of 2 nm
resulting from an in situ photofragmentation eect. In this context, the current work aims to
explore the liquid medium (water and toluene) eect on the Si-NPs structure and on the optical
properties of the colloidal solution. Si-NPs with high pressure structure (s.g. Fm3m) and
diamond-like structure (s.g. Fd3m), in water, and SiC moissanite 3C phase (s.g. F
%
43m) in toluene
are revealed by the means of High-Resolution TEM and HAADF-STEM measurements. Optical
investigations show that water-synthesized Si-NPs have blue-green photoluminescence emission
characterized by signal modulation at a frequency of 673 cm
1
related to electronphonon
coupling. The synthesis in toluene leads to generation of Si-NPs embedded in the graphitic
carbonpolymer composite which has intrinsic optical properties at the origin of the optical
absorption and luminescence of the obtained colloidal solution.
1. Introduction
Luminescent ultra-small silicon nanoparticles (Si-NPs) with
diameters in the range of 13 nm have triggered large research
activity with an outlook for various applications ranging from
light-emitting devices
1,2
and photovoltaic solar cell technology,
3
to uorescent biological label
4,5
and therapy.
6
Due to their
biocompatibility, high brightness and stability against photo-
bleaching, Si-NPs are considered to be ideal candidates for
substituting the uorescent dyes in bio-tagging and bio imaging.
7,8
They can also be integrated within the existing silicon technologies
for creating nanoscale optoelectronic devices.
3
Up to now, several
chemical
9,10
and physical methods
11
have been developed for
the Si-NPs synthesis. Compared to the physical method, the
solution chemistry route presents the advantages of controlling
simultaneously size and surface chemistry of NPs which is
required for NP functionalisation. However, such techniques
have the drawback of involving the use of chemical products
and reducing agents or require multi-step procedures for the
NPs size control.
9
Pulsed laser ablation in liquid (PLAL) is an
alternative approach for the fabrication of silicon nanoparticles.
1216
PLAL has some advantages: (i) a clean synthesis, without the
requirement of chemical precursors; (ii) simple, since it is performed
under ambient conditions; (iii) versatile, since the obtained NPs are
in colloidal solution form, giving the opportunity for further
nanoscale manipulations, such as biofunctionalization.
17
Photoluminescence (PL) properties of Si-NPs produced by
PLAL in various solvents have been reported. Svrcek et al. have
shown that the PL of Si-NPs obtained in water is located near
400 nm.
14
Lu et al. reported that the luminescence of Si-NPs in
toluene is in the visible range around 450 nm.
15
Recently, lumines-
cence measurements on Si-NPs prepared by PLAL in ethanol
displayed PL peak feature at around 630 nm.
16
Specically, it was
reported that similarity between PL of Si-NPs prepared in ethanol
with mean size between 2 and 3 nm and with mean size between 5
and 10 nm suggests a common origin, which is probably not due
to the pure size eect, i.e. quantum connement. These previous
works conrm that the liquid media in PLAL experiments have a
strong inuence on the optical properties of the obtained colloidal
solution. As a consequence, further investigations of the optical
properties of the colloidal solutions obtained by PLAL of silicon
in organic solvent are necessary in order to clarify a situation with
very high technological potentialities.
The production of small Si-NPs via PLAL has been inves-
tigated for dierent pulse durations and laser wavelengths.
Most of the studies report synthesis of small Si-NPs via the
PLAL method using nanosecond laser pulses, resulting in NPs
a
Nanophysics, Istituto Italiano di Tecnologia, via Morego, 30,
16163 Genova, Italy. E-mail: romuald.intartaglia@iit.it
b
Nanochemistry, Istituto Italiano di Tecnologia, via Morego, 30,
16163 Genova, Italy
c
Center for Biomolecular Nanotechnologies@UniLe, Istituto Italiano
di Tecnologia, via Barsanti, 73010 Arnesano, Lecce, Italy
w Electronic supplementary information (ESI) available. See DOI:
10.1039/c2cp42195j
PCCP
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This journal is c the Owner Societies 2012 Phys. Chem. Chem. Phys., 2012, 14, 1540615411 15407
which stabilize into clusters.
13,14
Post-chemical treatment of
the clusters is then required since most of the applications
need non-agglomerated nanoparticles.
13
Recently, our group
investigated the generation of Si-NPs by near-infrared femtosecond
PLAL demonstrating a size control mechanism dependent on the
laser pulse energy.
12
On the other hand, a widely studied
method to reduce the size of NPs, especially metallic, is the
photofragmentation, i.e., the fragmentation of large NPs into
small NPs by laser irradiation of the colloidal solution. NPs
photofragmentation has been investigated either ex-situ,
1821
i.e., by irradiation of the NPs colloidal solution or in situ,
2224
i.e., during NPs generation by PLAL.
Here, the UV picosecond laser ablation method is shown to
be a simple technique to prepare ultra-small and stable Si-NPs
with narrow size distribution in deionized water and toluene.
Characterization by Transmission Electron Microscopy
(TEM) and absorption spectroscopy reveals the generation
of Si-NPs with an average size of 2 nm. The nanoparticle size
results from the size-quenching eect due to an in situ photo-
fragmentation process. In this context, the current work aims
to explore the liquid medium eect on the silicon nanoparticle
structure and on the optical properties of the colloidal
solution. Si-NPs with high pressure structure (s.g. Fm3m)
and diamond-like structure (s.g. Fd3m), in water, and also
the SiC moissanite 3C phase (s.g. F
%
43m) in toluene are
revealed by the means of High-Resolution TEM and High
Angular Annular Dark Field Scanning TEM measurements
(HAADF-STEM), Energy Dispersive X-Ray Spectroscopy.
Optical analysis shows that Si-NPs synthesized in water have
blue-green photoluminescence emission, characterized by
signal modulation at a frequency of 673 cm
1
related to
electronphonon coupling. In the case of toluene liquid, our
experimental approach, consisting of the comparison of the
optical properties (absorption and PL) between the colloidal
solution obtained by PLAL and by the irradiated toluene
solvent without the silicon target, revealed that pulsed UV
irradiation of toluene generates a carbon based byproduct
(graphitic carbonpolymer composite) having staggering
optical properties matching with the ones of the colloidal
solution obtained by PLAL of silicon. This allows for the rst
time the clarication of the origin of the optical properties of
the colloidal solution obtained by UV PLAL of silicon in
toluene.
2. Experimental methods
2.1 Synthesis of Si nanoparticles
Synthesis of Si-NPs was carried out using a Continuum
Leopard laser providing pulses at 355 nm, with a time
duration of 60 picosecond, and at a repetition rate of 20 Hz.
The laser beam with a diameter of 6 mm is focused 10 mm
below the target surface using a lens with a focal length of
30 cm. Pulse energy was xed at 1 mJ. The silicon target
(99.999% from Alpha Aesar), in the form of a cylinder with a
diameter of 6 mm and a thickness of 10 mm, was placed on the
bottom of a quartz cuvette (dimension 10 10 30 mm
3
) and
immersed in 2 ml of liquid medium, either deionized water or
toluene (toluene spectrometric grade from Aldrich). The height
of the liquid above the target surface was 16 mm. Before each
experiment the target was mechanically polished and then
washed with the same liquid used for the ablation several
times to remove impurity from the surface. During laser
ablation, the target was moved using a rotation system to
achieve more uniform irradiation of the silicon surface. After
60 min of ablation, the solution was transparent for deionized
water, while it became brown for toluene solvent. As a control
test, both solvents were also irradiated without the presence of
a target, under the identical experimental conditions shown in
Fig. S1 (ESIw). The toluene solvent became brown, while water
did not change colour, as expected. All characterization
measurements were performed 1 day after preparation of the
colloidal solution.
2.2 Characterization
The Si-NPs colloidal solutions were deposited directly onto the
carbon-coated 300 mesh copper grid and were characterized by
Conventional TEM, High resolution TEM and High Angular
Annular Dark Field (HAADF) Scanning TEM (STEM) measure-
ments performed with a JEOL JEM-2200FS microscope, equipped
with a eld emission gun working at an accelerating voltage of
200 kV, a CEOS spherical aberration corrector of the objective lens
allowing to reach a spatial resolution of 0.9 A

, and an in-column
Omega lter. Chemical compositions were determined for several
NPs by Energy Dispersive X-ray Spectroscopy (EDS) analysis
performed in the STEM mode, using a JED-2300 Si(Li) detector
and using an electron probe of 0.7 A

size. A2 ml colloidal solution

was used to measure the absorption and photoluminescence
spectra. Optical absorption spectra were recorded in a quartz
cuvette (10 mm, Helma), using a cary 6000 UV-VIS double
beam spectrophotometer. The scan range was 200600 nm at a
600 nm min
1
rate. The photoluminescence (PL) measurements
for colloidal solution were carried out in the 350600 nm
wavelength range using a Fluoroma-4 Spectrouorometer
(JobinYvon-Horiba) tted with a photomultiplier and a Xenon
lamp source. PL and absorption spectra were corrected for
solvent contribution.
3. Results and discussion
3.1 Water-synthesised Si-NPs
The generation of Si-NPs by UV picosecond laser ablation was
investigated by systematic studies of the Si-NPs colloidal
solution produced at dierent irradiation times. Detailed
information about the morphology and size distribution of
the Si-NPs in water was obtained by TEM measurements.
Fig. 1 shows the TEM image of the Si-NPs obtained after
(a) 5 min and (b) 60 min of irradiation. For short ablation
time, the majority of the Si-NPs produced have an average size
of 10 nm as displayed in Fig. 1a. At longer irradiation time,
60 min, isolated Si-NPs i.e., non-agglomerated matrix free
NPs, with a spherical morphology are observed. The Si-NPs
size distribution, shown in the inset of the microphotograph,
was obtained considering more than 500 particles. The vast
majority of the produced NPs have very small size (average size
of B2 nm) but rarely larger NPs are also observed. From TEM
analysis of a bigger area (500 micrometer 500 micrometer,
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15408 Phys. Chem. Chem. Phys., 2012, 14, 1540615411 This journal is c the Owner Societies 2012
not reported), we can estimate that less than 1 percent of larger
NPs are present. The nanoparticle size reduction is attri-
buted to the well-known photofragmentation eect.
22,24
The
photofragmentation process is responsible also for the change
in color of the solution over time, varying from light yellow for
large size NPs with an absorption band up to 470 nm to
completely transparent for smaller size NPs with an absorp-
tion band below 300 nm.
12
Complementary to TEM analysis, HAADF-STEM,
EDX-STEM and HRTEM measurements were carried out
to determine the chemical composition and the crystalline
structure of the NPs. The HAADF-STEM image, presented
in Fig. 2a, shows the presence of ultra-small Si-NPs together
with a Si single particle (Si-SP) having a diameter of about
100 nm. Fig. 2b reports the EDX spectra of Si-SP and Si-NPs,
respectively, obtained by scanning the electron probe over two
regions of equal area. Both spectra reveal only the Si Ka peak,
but with dierent intensity because the signal of Si-NPs is
generated from a small scattering-volume with respect to that
of Si-SP. Fig. 2c shows the HRTEM images of Si-NPs having
diamond-like crystal structure (Fd3m) with the typical (111)
lattice sets and a d-spacing of 3.12 A

(Fig. 2c). Other crystal-

lites (Fig. 2d) exhibit lattice parameters and numerical electron
diraction patterns not consistent with the diamond-like
silicon, but compatible with a cubic silicon phase with space
group Fm3m characterized by smaller lattice parameters, and
are stable in high pressure, 80 kbar (PDF card 35-1158).
This is due to the conditions far from the equilibrium at
the local level provided by pulsed laser ablation in solution.
25
Due to the large dierence in temperature (10 000 K) and
pressure (about 1 GPa) between the hot plasma and the
surrounding medium, the growth of Si-NPs takes place inside
a high pressure cavitation bubble, leading to the formation of
cubic silicon phase.
Optical properties of Si-NPs synthesized in water after 60 min
of irradiation are reported in Fig. 3. A strong absorption band
in the UV range (black line) is observed corresponding to a
population with a size less than 3 nm
12
in agreement with the
corresponding electron micrograph analysis (Fig. 1b). Due to
the presence of NPs with size smaller than the Bohr exciton
radius in bulk materials, PL emission of water-synthesized
Si-NPs was observed. The PL spectrum shows peak emission
in the blue-green range at 460 nm, characterized by discrete
optical transitions. Theoretical and experimental investigation
relates the vibrational structure of photoluminescence i.e.
discrete transition, to the chemical nature of the NP surface.
For surface oxidized (carbide) Si-NPs, electronphoton coupling
between excitons and phonons of SiOSi (SiC) vibration
generates features in the emission spectra with a constant spacing
of 0.130.17 eV (0.18 eV).
2629
In the present case, the constant spacing between the
discrete structures is around 0.083 eV, which corresponds to
673 cm
1
, and it is attributed to the SiO bending vibrations
mode.
30
During the laser ablation process, the decomposition
of water molecules into O and OH

radicals occurs via

thermolysis due to extreme local temperature
31
as well as via
Fig. 1 TEM images of Si-NPs synthesized in water via UV PLAL
after (a) 5 min and (b) 60 min of irradiation.
Fig. 2 (a) HAADF STEM image displaying both a bigger single
particle Si-SP and ultra small Si-NPs synthesized in water, red and
cyan squares highlight, respectively, the two regions scanned for the
areal STEM-EDX analyses, and (b) corresponding EDX spectra, red
for the Si-SP and cyan for the Si-NPs, showing only the presence of Si
Ka peaks. HRTEM images of obtained Si-NPs via UV picosecond
laser ablation in water. (c) Single Si-NP synthesized in water showing
the (111) lattice sets with a d-spacing of 3.12 A

, characteristic of silicon
with Fd3mstructure. (d) Single Si-NP synthesized in water showing the
(111) and (022) lattice sets with d-spacings of 2.25 A

and 1.38 A

,
respectively, the numerical electron diraction pattern (inset) is
compatible with the [0
%
1 1] zone axis projection of Fm3m structure.
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photolysis due to near UV irradiation through two-photon
absorption.
32
3.2 Toluene-synthesised Si-NPs
Laser ablation of the silicon target in toluene solvent is
investigated in order to clarify the eects on the structural
and optical properties of the resulting colloidal solution, e.g.
strong photoluminescence response as that reported in ref. 15.
Fig. 4a shows a TEM image of the Si-NPs synthesized in
toluene via PLAL after 60 min of UV irradiation under the
same laser pulse energy conditions used for Si-NPs generation
in water. Si-NPs are found to be ultra small with a mean size of
around 2 nm. HRTEM data analysis revealed the nucleation
of rare Si-NPs exhibiting lattice parameters compatible with
the Si moissanite 3C phase with space group F
%
43m (PDF card
75-0254). An example of single SiC NPs is shown in Fig. 4c
where the lattice sets (1
%
11) and (220) of moissanite 3C are
displayed. The formation of SiC-NPs results from a decom-
position of the solvent, similarly to what has been found by
PLAL of silicon in ethanol solvent.
16
Moreover, some crystal-
lites synthesized in toluene exhibited lattice parameters and
numerical electron diraction patterns compatible with a
cubic silicon phase with space group Fm3m characterized by
smaller lattice parameters, and stable under high pressure
conditions, 80 kbar (PDF card 35-1158) (Fig. 4b), as observed
for Si-NPs generated in water.
In contrast to the case of the PLAL in water, a black solid
lm surrounding Si-NPs is also observed. The generation
of NPs embedded in the carbon byproduct and carbide
compound via PLAL has been previously reported.
3335
The
formation of carbon byproduct has been attributed to a
reaction between the solvent molecules with the plasma plume
during the ablation process.
34
In particular, Yang et al.
35
have
reported the generation of carbon byproduct by laser ablation
of the silicon target in toluene solvent, as revealed after post-
treatment of the colloidal solution by centrifugation in order
to remove the Si-NPs. The resulting supernatant, i.e., carbon
byproduct colloidal solution, has been shown to have lumines-
cence properties. Similarly, it has been reported
15
that the
colloidal Si-NPs solution obtained via PLAL in toluene has
emission properties similar to the supernatant solution
reported in ref. 35. However, all these observations still lack
control experiments, i.e., the irradiation of the solvent without
the target under the same experimental conditions used for
PLAL experiments, in order to better understand the process
underlining the production of carbon byproduct.
We did perform the control experiment with the toluene
solvent, as reported in the schematic of Fig. S1 (ESIw). The
TEM image of the irradiated toluene solvent after 60 min of
irradiation without the presence of a target is reported in
Fig. S2 (ESIw). It shows the presence of a carbon byproduct
lm similar to the one shown in the electron micrograph of the
colloidal solution obtained by PLAL of silicon in toluene
(Fig. 4a). This indicates that the toluene molecules interact
directly with the 355 nm laser wavelength during the irradia-
tion process, resulting in a modication of the chemical/
molecular structure of the solvent. This photochemical process
is based on photolysis of toluene molecules, and the nature
of the products is strongly dependent on the experimental
conditions (pressure/temperature) as well as on the laser
wavelength.
36
Photochemical reactions like CH, CC ssions
Fig. 3 Optical properties of the Si NPs colloidal solution via UV
picosecond laser ablation in water after 60 min of irradiation, absorp-
tion spectrum (black line) and PL spectrum (red line). Excitation
wavelength used for PL measurement: 290 nm.
Fig. 4 (a) TEM image of the Si-NPs colloidal solution obtained via
PLAL in toluene. Solid black lm corresponds to the graphitic
carbonpolymer composite, generated by photodecomposition of the
toluene solvent. (b) HRTEM image of single Si-NPs showing the (111)
and (200) lattice sets with d-spacings of 2.25 A

and 1.95 A

, respec-
tively, the numerical electron diraction pattern (inset) is compatible
with the [0
%
1 1] zone axis projection of Fm3m structure. (c) HRTEM
image of a single moissanite 3C crystal observed along its [
%
1 1 2] zone
axis, as conrmed by the numerical electron diraction pattern (inset),
and exhibiting the typical lattice sets (1
%
11) and (220) with d-spacings of
2.51 A

and 1.54 A

respectively.
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15410 Phys. Chem. Chem. Phys., 2012, 14, 1540615411 This journal is c the Owner Societies 2012
take place during UV irradiation leading to the generation of
graphitic carbon and polymeric C/H agglomerates formation.
Optical properties of both carbon byproduct, generated by
the irradiation of toluene solvent, and the colloidal solution
obtained by PLAL of silicon in toluene were investigated and
compared. Fig. 5a display the absorption spectra of the fresh
toluene solvent (dotted green curve), UV irradiated toluene
solvent (blue curve) and Si-NPs colloidal solution synthesized
in toluene (red curve). Firstly, the absorption spectrum of the
irradiated toluene solvent shows a clear red-shift of the
absorption edge with respect to the one of the fresh toluene
solvent. Thus, the carbon byproduct generated by UV irradia-
tion of toluene solvent without the target has a distinct optical
absorption spectrum with respect to the starting solvent.
Secondly, Si-NPs colloidal solution synthesized in toluene
displays an absorption edge with a cut-o in the same wave-
length range as that for the irradiated toluene solvent (around
450 nm).
Since the elements constituting the colloidal solution are the
carbon byproduct and ultra small Si-NPs, the latter having an
absorption cut-o of around 300 nm (Fig. 3), the observed
absorption properties are attributed to the carbon byproduct.
This proves that the absorption properties of Si-NPs colloidal
solution synthesized in toluene arise from the carbon byproduct
and not from Si-NPs. Further experimental works are in
progress to give an insight into the molecular structure of
the carbon byproduct obtained by 355 nm picosecond laser
irradiation of toluene.
Fig. 5b shows PL spectra of the toluene solvent (doted green
curve), UV irradiated toluene solvent (blue curve), and Si-NPs
colloidal solution synthesized in toluene (red curve). No PL
emission was observed for the non-irradiated toluene solvent
(the small peak around 390 nm originating from Raman
emission). The irradiated toluene solvent instead has PL
emission in the visible range with a peak at around 420 nm.
Thus, the carbon byproduct generated by UV irradiation of
toluene solvent has intrinsic luminescence properties. Si-NPs
colloidal solution synthesised in toluene has a luminescence
spectrum similar to the irradiated toluene solvent, only the PL
intensity is slightly higher. This may indicate that silicon
ablation plays a role of a catalyser increasing the amount of
the carbon byproduct, and consequently the luminescence
intensity. It is stressed that the perfect match found between
the PL spectrum from colloidal solution obtained by PLAL of
silicon in toluene and irradiated toluene explains the origin of
previously reported luminescence properties.
15
In summary, the mechanism behind the generation of
carbon byproduct by PLAL in toluene solvent, which may
nullify the inherent purity of the laser based method, is quite
complex and needs to be investigated more in detail. It has
been suggested that the carbon byproduct results from an
interaction between solvent molecules and species present in
the ablation plasma plume.
34
Our approach, based on the
control experiment without the target and on detailed optical
investigations, reveals that other mechanisms have to be taken
into account, such as direct interaction between solvent mole-
cules and laser. This allows for the rst time the distinction of
the basic optical properties (absorption and PL) between the
carbon byproduct and the generated Si-NPs constituting the
colloidal solution in UV PLAL of silicon in toluene.
4. Conclusion
It is shown that UV picoseconds pulsed laser ablation of a
solid target in liquid is a simple technique to synthesize
luminescent ultra-small (23 nm) and well-dispersed Si-NPs.
The obtained ultra small size results from an in-situ photo-
fragmentation mechanism. Liquid media are found to inuence
the microstructure of the obtained Si-NPs and on the optical
properties of the colloidal solution. Si-NPs with high pressure
structure (s.g. Fm3m) and diamond-like structure (s.g. Fd3m) are
observed for water. For toluene, besides Si-NPs, also SiC-NPs
with moissanite 3C phase (s.g. F
%
43m) are observed. PL studies
show that the water-synthesized Si-NPs present very specic
blue-green emission characterized by signal modulation at a
frequency of 673 cm
1
related to electronphonon coupling.
Laser synthesis in toluene solvent leads to the formation of
Si-NPs embedded in a graphitic carbonpolymer composite
originating from the interaction of the toluene molecules with
the UVphotons. Detailed optical investigations demonstrate that
the optical absorption and broad PL of toluene-synthesized
Si-NPs obtained by PLAL arise from the graphitic carbon
polymer composite and not by the generated Si-NPs.
Fig. 5 (a) Absorption spectra of the fresh toluene solvent (dotted
green line), UV irradiated toluene solvent (blue line) and Si NP
colloidal solution synthesized in toluene (red line), after 60 min of
irradiation. (b) PL spectra of the fresh toluene solvent (dotted green
line), UV irradiated toluene solvent (blue line) and Si colloidal solution
obtained via PLAL in toluene (excitation wavelength: 350 nm).
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This journal is c the Owner Societies 2012 Phys. Chem. Chem. Phys., 2012, 14, 1540615411 15411
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